Polyisocyanate composition and process for treating cellulosic materials therewith to render them water repellant

ABSTRACT

A METHOD FOR RENDERING CELLULOSIC MATERIALS WATER-REPELLENT BY CONTACTING THE CELLULOSIC MATERIAL TO BE TREATED WITH AN EMULSION FORMED BY A SOAP, A SURFACE ACTIVE AGENT AND A POLYARYL POLYISOCYANATE CONTAINING AT LEAST THREE ARYL GROUPS AND AN AVERAGE OF AT LEAST THREE ISOCYANATE GROUPS, A PORTION OF WHICH MAY BE MODIFIED BY REACTION WITH AN ALCOHOL, THIALCOHOL, ORGANIC ACID, AMINE OR AMIDE, AND THEREAFTER CURING THE TREATED MATERIAL WITH WATER.

United States Patent Oflice 3,672,818 Patented June 27, 1972 POLYISOCYANATE COMPOSITION AND PROCESS FOR TREATING CELLULOSIC MATERIALS THEREWITH TO RENDER THEM WATER RE- PELLANT George M. Wagner, Lewiston, and William J. Vullo,

Burnt Hills, N.Y., assignors to Hooker Chemical Corporation, Niagara Falls, N.Y.

No Drawing. Original application July 30, 1969, Ser. No. 846,283, now Patent No. 3,617,189. Divided and this application Nov. 25, 1970, Ser. No. 92,856

Int. Cl. D06m 13/42 US. Cl. 8-1162 6 Claims ABSTRACT OF THE DISCLOSURE A method for rendering cellulosic materials water-repellent by contacting the cellulosic material to be treated with an emulsion formed by a soap, a surface active agent and a polyaryl polyisocyanate containing at least three aryl groups and an average of at least three isocyanate groups, a portion of which may be modified by reaction with an alcohol, thioalcohol, organic acid, amine or amide, and thereafter curing the treated material with water.

This is a divisional application of Ser. No. 846,283, filed July 30, 1969, now US. Pat. No. 3,617,189.

This invention relates to an improved composition and process for treating cellulosic materials and more particularly, it relates to an improved composition and process for treating cellulosic materials so as to render them highly water repellent.

In the past, considerable time and effort has been expended in the development of compositions and processes for treating cellulosic materials so as to render them water repellent. Although many compositions and processes for this purpose have been developed and used, for the most part none of these have been completely durable to repeated launderings and/ or dry cleanings. Accordingly, cellulosic textile materials which have been treated with the prior art compositions to render them water repellent frequently loose this water repellency and must be retreated to restore it after several dry cleanings or Washings. Additionally, insofar as the cellulosic textiles are concerned, problems have sometimes been encountered in that the prior art water-repellent compositions have adversely altered the hand of the fabric, making them hard and/or stiff and boardy. Moreover, and particularly with regard to the treatment of paper, the cost of the prior art water repellency compositions and processes has frequently been sufficiently great as to discourage their wide spread acceptance and use.

It is, therefore, an object of the present invention to provide a novel treated cellulosic material which is substantially permanently water repellent.

A further object of the present invention is to provide an improved process for treating cellulosic materials so as to render them substantially permanently water repellent, which process is easily and economically carried out.

These and other objects of the present invention will become apparent to those skilled in the art from the description which follows.

Pursuant to the above objects, the present invention includes a process for treating a cellulosic material which comprises contacting the cellulosic material with a polymerizable treating solution comprising a polyaryl polyisocyanate containing at least three aryl groups and an average of at least three isocyanate groups, a portion of which isocyanate groups may be modified by reaction with an alcohol, thioalcohol, organic acid, amine or amide, and

thereafter, curing the thus-contacted material with water.

The cellulosic materials, including cellulosic textiles and paper, treated in accordance with this process are found to be durably water repellent, even after repeated dry cleaning or washing in hot water. Additionally, the hand or feel of the thus-treated cellulosic textile materials is generally found to be substantially unchanged from that of an untreated material.

More specifically, in the practice of the present invention, the cellulosic material to be treated include cellulosic textile materials, such as cotton, ramie, rayon, jute, and non-textile materials such as paper, cardboard, wood, and the like. These cellulosic materials may be in various forms, including yard or sheet goods, as well as various finished articles, such as articles of clothing, including coats, shirts, trousers, skirts, and the like, and such nontextile articles as paper containers, bags, wallboard and the like. Of the numerous cellulosic materials with which these articles may be made, the process of the present invention has been found to be particularly applicable in the treatment of cotton and paper. Accordingly, hereinafter, primary references will be made to cotton and paper as being the preferred cellulosic materials. This is not, however, to be taken as a limitation on the present invention as other cellulosic materails may also be advantageously treated by the present process. Additionally, the process of the present invention is not limited to the treatment of cotton, paper or other cellulosic materials in the form of yard or sheet goods or finished articles, but may, in many instances, also be utilized in treating these materials in the fiber, yarn or pulp form.

In treating the cellulosic material so as to make them durably water-repellent, the material is impregnated with a solution which comprises, as the essential Water repellent component, a polyaryl polyisocyanate compound, either as such or modified by reaction with an alcohol, thioalcohol, organic acid, amine or amide. Suitable compounds may be characterized generally as being selected from the group consisting of wherein n is a number having an average value of at least 1 and is generally from 1 to 4; t is a number from 2 to 4; p is a number from 0 to 2; p is 0 to 1; t+p has an average value of at least 3 and is generally from 3 to 4; t+p+p is 4; m is a number from 0 to l; R is selected from the group consisting of halogen, hydrogen, alkyl and alkoxy; y is selected from the group consisting of hydrogen, alkyl and phenyl; R is selected from the group consisting of OX, SX, X,

0 MN/ and X i JN and X 18 selected from the group consisting of hydrogen, alkyl, alkylphenol, alkylphenoxyal-koxy and phenyl.

Desirably in the compounds used, as characterized by the above generic formulas, the alkyl groups, either as such or in an alkylphenoxy or allkoxy group contain from about 1 to 20 carbon atoms and preferably from about 4 to 20 carbon atoms. Additionally, the term halo- NCO IIIC O I CH NCO AGE:

I|-IOO HIIIC-OCaHs IFTCO EN -O C18H31 11100 I l t J, t

NCO

gen, as used in the formula, is intended to include ehlorine, fluorine, bromine and iodine. Exemplary of specific compounds falling within the generic formulas given hereinabove are the following:

IIICO IIICO zoHn lzoHn 20H ITYCU Ha 6H3 CH; 4 OOHa IIIC O I C H: @CHy-GCHr-Q 1 l I v It is to be appreciated that similar compounds, other than those which have been specifically set forth hereinabove, may be utilized as water repellent agents in the process of the present invention. Additionally, the water repellent compositions used may be a mixture of one or more of the above compounds or other similar compounds which fall within the generic formulas which have been given. Often, such mixtures will be the natural result of the preparation of the compositions, which preparations may give a statistical distribution of the possible products. Such mixtures may be mixtures of various polymethylene polyphenyl isocyanates, mixtures of various poly(isocyanatophenyl)methanes, or mixtures of both polymethylene polyphenyl isocyanates and poly(isocyanatophenyl)methanes.

In preparing the impregnating solutions for use in the NCO method of the present invention, the water repellent component as has been described is dispersed or dissolved in a suitable solvent. Although any solvent, in which the isocyanate material will dissolve without decomposition may be used, in many instances, the aromatic organic solvents, such as benzene, toluene, xylene, and the like, are preferred. Additionally, halogenated aliphatic solvents, such as trichloroethylene, perchloroethylene, carbon tetrachloride, methylene chloride, and the like, have also been found to be extremely useful. The solvents may be classified generally as benzene, substituted benzenes containing 1-3 lower alkyl groups of 1-6 carbon atoms each and halogenated lower alkyls containing 1-6 carbon atoms and 1-8 halogens. The water repellent component is dispersed or dissolved in the solvent in an amount sufficient to provide the desired resin add-on on the cellulosic material when the material is impregnated with the solution. Concentrations within the range of about 0.5 to about 50% by weight of the solvent composition are typical, but in many instances, higher concentrations are also suitable, up to the maximum solubility of the isocyanate material in the solvent used. Typical of such higher concentrations which may be used are those of 80 to 90% by weight of the solvent composition, or even higher, in those instances where the isocyanate material used is miscible in substantially all proportions with the solvent.

In preparing the impregnating solution for use in the present method, when using 'an unmodified polyisocyanate, such as polymethylene polyphenylisocyanate or tris(isocyanatophenyl)methane, the polyisocyanate material is dissolved in the solvent in an amount sufficient to provide the desired concentration in the impregnating solution. Where a modified polyisocyanate material is used, the unmodified polyisocyanate may be dissolved in several times its own weight of solvent and to this mixture the modifying material, such as an alcohol, thioalcohol, organic acid, amine, or amide is added, in an amount suflicient to react with the unmodified polyisocyanate and effect the modification desired. Additionally, if desired, the reaction mixture may also contain a suitable catalyst, such as a polyalkyl amine. Typically, the amount of modifying agent added is sufficient to react with from about to about 70% of the isocyanate groups present, and preferably is sufiicient to react with from about to 35% of the isocyanate groups. The amount of modifier used is such that in the resulting modified isocyanate there are at least two unmodified isocyanate groups.

Once the reaction is substantially complete, additional solvent may be added to the reaction mixture to obtain the impregnating solution having the desired concentration. Alternatively, of course, the modified polyisocyanates may be prepared separately and thereafter dissolved in the solvent in appropriate amounts to form the impregnating solution, as is done with the unmodified polyisocyanate.

Additionally, it is to be appreciated that the water repellent compositions of the present invention may be applied as an emulsion, rather than as a solution. In such instances, the polyisocyanate as such or modified as has been indicated above is admixed with a suitable emulsifying agent and dispersed in water. These emulsion systems, like the solutions, may contain from about 0.5 to 50% by weight of the polyisocyanate material, with the higher concentrations also being usable. For many applications, however, emulsion systems having a solids content of from about 1-15% by weight are preferred. Suitable emulsifying agents which may be used are anionics such as the alkyl and alkyl aryl sulfonates and sulfates and nonionics, such as the alkylene ethers. Typically, the anionics will contain from about 4 to about 30 carbon atoms in the alkyl portion and from 6-10 carbon atoms in the aryl portion. The nonionics will typically contain from about 4 to about 30 carbon atoms and from about 1 to moles of alkylene oxide. In many instances, it has been found to be desirable to include a fatty acid soap in the emulsion. Such soaps typically contain from about 8 to about 26 carbon atoms and are exemplified by the metal stearates, palmitates and the like. The term alkali metal is intended to include sodium, potassium, lithium, cesium and rubidium.

A typical emulsion containing 10% solids for use in the present method will contain the following components in the amounts indicated:

Components: Parts by weight Polyisocyanate composition (as a 35% solution in toluene) 2.85-285 Soap 0.3-3

Surface active agent 0.2-1.0

Water-balance to make 100 12 If desired, this emulsion may be further diluted with water, emulsions having a solids content as low as 0.1% having been found to be useful. It is to be noted that in this emulsion, it is desirable that the surface active agent is present in the minimum amount needed to hold the emulsion. In this manner, the rewetting effect of the surface active agent is minimized. Additionally, the presence of the soap is found to aid in forming and holding the emulsion and also in reducing the rewetting effect.

The cellulosic materials, such as a cotton textile material or paper, may be impregnated with the polymerizable solution or emulsion prepared as indicated hereinabove, using any convenient means. For example, the cotton may be immersed or padded in the treating solution or emulsion and the fabric then passed through squeeze rolls to remove excess solution. If desired, as with paper, the treating emulsion or solution may be applied to the paper by spraying, rather than by immersion. Other suitable application techniques, as are known to those in the art, may also be used. After the cellulosic materials have been impregnated with the emulsion or solution, they are preferably dried so as to remove the solvent from the material. Desirably, the impregnation is carried out so that the treated cellulosic material has a resin add-on within the range of about 1 to about 15% by weight of the material. Higher resin add-on than 15%, e.g., 40 to 50%, may be attained in some instances although, generally, it has not been found that such higher add-ons appreciably improve the water repellency which is obtained. Generally, it has been found that resin add-ons appreciably less than 15%, e.g., 0.05 to 5% are often sufficient to provide durable water repellency of the cellulosic materials, Typically, the treating solution or emulsion is maintained at a temperature within the range of about 10 centigrade to the boiling point of the solvent used, e.g., centigrade for perchloroethylene, and preferably is within the range of about 20 centigrade to about 30 centigrade during the impregnation step. Thereafter, the impregnated material is dried, preferably in an oven, at a temperature within the range of about 20 centigrade to the boiling point of the solvent used, with temperatures within the range of about 65 centigrade to about centigrade being preferred.

Following the impregnation and drying of the cellulosic material, the thus-treated material is then cured in water. Although various techniques may be utilized in eifecting this cure, where the treated material is a cellulosic textile, the material is preferably immersed in water, and maintained in the water until the curing is complete.

It has been found that the time to effect the desired cure of the polyisocyanate material with which the cellulosic textile is impregnated varies with the temperature at which the cure is effected. Accordingly, it is desirable that the water used is at an elevated temperature, temperatures within the range of about 40 centigrade to about 100 centigrade being typical, with temperatures within the range of about 80 centigrade to about 94 centigrade being preferred. When carrying out the water cure at these temperatures, curing times within the range of about 1 hour to about 1 minute are typical, with times of 30 minutes to 2 minutes being preferred. It is to be appreciated, that where the length of curing time is not an important factor, the water cure of the polyisocyanate impregnantmay be carried out at room temperature, i.e., about 20 centigrade. Under such conditions, the curing time may be as long as several days, e.g., 48 hours. There is, however, some indication that the full water repellency effectiveness of the polyisocyanate compositions may not be attained when the water cure' is carried out under these low temperature conditions. Moreover, it has been found that low temperature curing techniques, and particularly those carried out below about 75 centigrade, may not impart to the treated fabric the desired degree of durability to dry cleaning solvents, such as trichloroethylene. In many instances, after curing under these conditions, dry clean- 13 ing of the fabric may remove appreciable quantities of the cured water repellent material, Accordingly, low temperature curing techniques are generally not preferred for cellulosic textiles.

It is to be further appreciated, that if desired, the water cure of the polyisocyanate impregnant in either a textile or non-textile material may be effected by substantially saturating the impregnated cellulosic material with Water and thereafter, completing the polymerization or cure of the polyisocyanate by heating the water-wet, substantially saturated material at an elevated temperature. In such processes, curing temperatures within the range of about 66 centigrade to about 177 centigrade for periods of about 30 minutes to about 1 minute are typical, with temperatures within the range of about 107 to about 135 centigrade for periods of minutes to about 3 minutes being preferred. After the water cure of the impregnated material has been completed, the material is then dried to remove any water which may remain. Frequently, when using water impregnation of the treated material, followed by heating at an elevated temperature, the curing and drying of the impregnated material is effected substantially simultaneously.

It has further been found that in some instances water in vapor form may be used to effect the cure of the impregnated cellulosic material. Such water may be as steam, water vapor or the like, including water vapor in the atmosphere. The use of water in this form has been found to be of value in curing impregnated paper. In such a process, the paper which has been impregnated with the treating solution or emulsion is then brought into contact with Water vapor, as for example in an area of relatively high humidity and cured either with or without the application of heat. In many instances, it has been found sufiicient if the paper is cured at room temperature in the atmosphere. Such a curing technique is satisfactory for paper or other cellulosic materials which, during use, will not be subjected to repeated washing and/or dry cleanings and which, normally, will not be reused numerous times. In such materials, any reduction in durability of the impregnant due to the way the water cure is carried out will not be of great consequence.

It has been found that in many instances the water used to carry out the polymerization or cure of the polyisocyanate impregnant in the textile material is desirably slightly alkaline. Typical pH values for the curing water are within the range of about 7.5 to 9. Where the pH of the curing water is below these values, it may be adjusted by adding thereto an alkaline material, such as an alkali metal bicarbonate. Additionally, if desired, the curing water may also contain small amounts of a suitable wetting agent, to insure more thorough and rapid wetting of the impregnated material. Typical wetting agents which may be used are nonionics, such as the polyalkylene ethers and anionics such as alkyl aryl sulfonates and sulfates. These materials are typically present in amounts Within the range up to about 1% by weight of the treating water, amounts within the range of about 0.05 to about 0.2% being preferred.

As has been indicated hereinabove, the process of the present invention may be carried out on cellulosic materials in various forms, including yard or sheet goods, finished articles, such as coats and the like, as well as on pulp, the unspun tfiber or the yard itself. It has been found that cellulosic materials, such as cotton and paper, which have been treated in accordance with this process consistently show excellent water repellency, and the wet strength and burst strength of treated paper is also good. Moreover, it has been found that the water repellency is retained by the treated fabrics even after numerous washings in hot Water and that the hand and feel of the treated materials are not substantially different from those of untreated material. Additionally, the water repellent finish is durable to dry cleaning and is found to im- 14 part dimensional stability to the fabric. It also facilitates dyeing and improves dye fastness.

In order that those skilled in the art may better understand the present invention and the manner in which it may be practiced, the following specific examples are given. It is to be understood that these examples are illustrative of the invention and are not intended to be limitations thereon. In these examples, unless otherwise indicated, temperatures are in degrees Centigrade and parts and percentages are by weight. Additionally, in these examples, one or more of the following tests are used to evaluate the treated materials:

(1) Spray testFederal Specification ccc-T-19 l-6-A #5526 or American Association of Textile Chemists and Colorists-#22-l964.

250 milliliters of water are sprayed downwardly, though a standard nozzle, on the sample which is held at a 45 angle to the horizontal. The degree of wetting is compared to standard photographs. is excellent-no Wetting and 0 is complete absorbency.

|(2) Hydrostatic testFederal Specification ccc-T-1916- #55121.

The amount of water, in grams, is measured which penetrate the sample in .10 minutes at a hydrostatic head of 8 inches.

(3) Impact penetration test-Federal Specification ccc- T-1916-#5522.

The amount of water, in grams, is measured which penetrates the sample when 500 milliliters of water are sprayed on the sample from a length of 2 feet. I

(4) Water absorbency test-American Association of Textile Chemist and Colorists 21-1964.

The weight percent of water which is absorbed by the sample during a 24 hour immersion in water is measured.

(5) Methanol/ water testThe specimen is contacted for 15 seconds with various methanol-water solutions containing from 0 to 100% by volume methanol. Specimen is given a rating corresponding to the methanol content of the solution which just doesnt wet the surface of the specimen. 0 is the lowest rating-no water repellency and 100 is the highest.

(6) Bag test-The fabric is shaped to form a bag and water, to a depth of 4 inches, is added. Leakage during 24 hours is noted. If no leakage occurs, fabric is rated as passing. If there is leakage, fabric is noted as failing.

(7) Tensile strength test-Carried out on a Scott Tensile Tester using a jaw opening of 3 inches, a rate of travel of 12 inches per minute and measured in the machine direction. Results are in pounds/inch of width of the specimen.

(8) Burst testCarried out on a Mullin Burst Tester using technical Association of Pulp and Paper Institute Test T-403m-53. Results are in pounds/square inch.

Additionally, in the Wet Gurley stiffness, wet tensile strength and wet burst strength tests, the properties were determined after the specimen had been immersed in water for 24 hours.

EXAMPLE 1 A treating solution was prepared by dissolving a commercial polymethylene polyphenylisocyanate, having a viscosity of 250 centipoises at 25 C., and an NCO equivalent weight of 133.5, in benzene to form a solvent solution containing about 3% by weight of the polyisocyanate. 79 pound kraft paper was impregnated with the solution to a wet pick-up of 55%. The paper was then airdried, immersed in water for 10 minutes and then heated at C. until dry to effect simultaneous curing and drying. The resin add-on on the paper was 1.9%. One portion of the thus-treated paper was placed in boiling 15 water for 24 hours and this portion and a treated but unboiled portion were tested for impact penetration, and wet and dry tensile strength. The following results were obtained:'

16 After 9 boil cycle s,-the fabrics were retested and the results obtained were as follows:

Unboiled Boiled A B Impact penetration rams) 0 0 Spray rating 50 60 50 Dry tensile strength Epounds per inch of width) 63 59 Impact penetration test (grams)- 0 0 0 Wet tensile strength (percent of dry) 31 25 Hydrostatic test (grams) 0 0 Y 0 In contrast, an untreated control disintegrated almost immediately in the boiling water.

EXAMPLE 2 The procedure of Example VI was repeated but using a trichloroethylene solution of the polyisocyanate at varying concentrations. The treatedpaper samples and an untreated control were then tested to determine the extent of water repellency and the following results were obtained:

EXAMPLE 4 A treating composition was prepared by dissolving 50 parts of the polymethylene polyphenylisocyanate, as used in, Example 1, in 100 parts of toluene. *To this solution were. added parts of l-octadecanol, and 0.5 part of triethylamine catalyst. The resulting solution was stirred for a period of about 30 minutes while the temperature was maintained below about 40 centigrade. At the end A polyisocyanate treating solution was formed as in Example 1. This solution, at various concentrations was padded onto 8.5 ounce sateen cotton to obtain a wet pick- A B 0 D 20 Solution concentrations (percent) 1.0 0.6 0.1 f thls F It found that an of the alcohol a et p c up 23 2g 18 acted withthe lsocyanate to form an alcohol substituted ra T8111 Hpydgostaticgtestfigmmsyn 0 0 0 (2) polyisocyanate contalmng 0.2 mole of alcohol per mole .gnpacklgenetgatioil (grams)- 3 3 (2 equivalent of NCO group. A series of dllute treating solua 81 sorp 1011 DGI'CBII Dry tensile strength (pounds per inch of width). 70 67 67 62 l were Prepared and applied to 80 Pound kraft Paper Wet tensile gtrengfih (percgnt of dry) l 22 1 g 8 as 1n Example 1. The treated paper samples were then @3835; g fggg $33 15 g;f f f f2:: 2 31 2 cured as in Example 1, dried and tested to determine the ,Untmatei effectiveness of water repellency treatment. The results of I Sample failed. these tests were as follows:

Add-on, percent 0.1 0.5 1.0 2.0 3.0 4.0 5.0 10 20 30 Untreated Water resistance:

Spray rating 60 65 90 95 95 95 95 95 100 100 100 0 Hydrostatic (grams) 0 0 0 0 0 0 0 0 0 O 0 Fail Impact penetration (grams). 0 0 0 0 0 0 0 0 0 0 0 Fail Water absorption, percent. 59 54 52 48 47 49 54 54 52 49 41 115 Methanol/water 60 70 70 80 70 80 80 80 80 70 70 0 Tensile strength, (pounds per inch of width):

Dry 59 57 63 63 63 63 68 73 74 72 67 62 Wet, percent ct dry 15 24 22 21 .24 22 22 22 25 2s 29 s Bursting Strength, (pound per square inch).

Dry 74 64 71 61 66 64 77 75 72 73 79 60 Wet, percent of dry 21 29 35 39 41 39 37 41 45 48 14 Stiffness, Gurley (milligrams) Dry 1,354 1,350 1,420 1,490 1,755 1,710 1,755 1,600 1,619 1,930 1,800 1,510 Wet, percent of dry. 27 21 21 23 23 23 26 26 26 29 23 EXAMPLE 3 EXAMPLE 5 Additional treating solutions were formulated, using the procedure of Example 4 with the exception that five, ten, fifteen and thirty parts by weight of the alcohol were up of about 65%. The fabrlc was air dried and then cured 9 by lmmerslon in water at 50 C. for 10 minutes. Thereused. The resulting alcohol substituted polyrsocyanates g tg the f i h fabntcs Wereutested ig fi formed contained 0.05, 0.10, 0.15 and 0.30 mole of alcon e in e co lveness o e Y repe ency a o Ow g hol per mole equivalent of NCO. Treating solutions were results were obtained.

formed as in Exam 1e 4 and kraft a er sam les were A B 0 treated to obtain varying resin add-ons. After curing and Solution concentration (percent) 1O 7. 5 5.0 .Resin add-0n (percent)- as 6.7 2.6 drying, these samples were lncluded 1n the tests of the Spray rating 60 Impact penetration test (grams) 0 0 0 samples of Example 4 and the followmg results were Hydrostatic test (grams) 0 0 0 obtamed:

Tensile Burst Water Strength Percent Impact Spray Hydroabsorption, Wet, percent Strength wet, peradd-on. test rating static percent Dry of dry dry cent of dry Polyisocyanate modifier:

0.05 moles of alcohol--. 1. 0 0 95 0 41 68 31 62 19 Do 0.5 0 0 41 63 20 60 17 Do 0.1 0 60 0 46 68 20 62 13 0.10 moles of alcohol .1. 0 0 0 42 67 27 57 19 Do 0.5 0 95 0 41 64 25 62 15 Do 0.1 0 60 0 44 61 23 54 14 0.15 moles of alcohol.... 1. 0 0 0 40 68 27 57 19 Do 0.5 0 95 0 40 68 25 66 14 Do 0.1 0 75 0 44 71 20 60 13 0.30 moles of alcohol 1.0 0 100 0 33 58 43 56 22 Do 0.5 0 90 o 36 59 2s 68 20 Do 0.1 0 60 0 Y 41 59 21 66 14 1 7 EXAMPLE 6 The procedure of Example 4 was repeated using 1- butanol, l-octanol, l-dodecanol and tetradecanol as the as in that example. The results of these tests were as follows:

modifying alcohols, in amounts of 5.46, 9.6, 13.7 and Add-n, percent 0.1 1.0 15.8 parts by weight, respectively. The resulting mod1- Water resistance: fied polylsocyanates all contained about 0.2 mole of alcoprgy n rti g 6g 63 y l'OS a hol permole equlvalent of NCO. After treating kraft paper Impact penetration n 0 with solutions of these products, as in Example 4, the Wattrabsorptiollmercent 66 mples were cured in air 24 hours at room temperature l gggggg gggg and hen treated for water repellency and the following 10 ri a l 62.12

. e ,percen y results were obtained. Bum Strength.

Dry 71 73 Wet, percent of dry 18.3 23. 3 Stifiness, Gurley:

Dry 1, 090 1,890 Wet, percent of dry 4 17. 8

Percent solids in Water ab- Hydro- EXAMPLE 9 treating Methanol- Spray sorption, static Product solution water test rating percent test A treatmg composition was prepared as in Example 4. 24 50 7H0 36 0 This composition was formed into a treating solution in CaHnOH--- 2.6 60 80 35 0 trichloroethylene containing 4.0% of the modified poly- C1zH2sOH. 2. 7 80 90 37 0 CHHHOH" 28 80 90 38 0 lsocyanate. Samples of cotton cloth were passed through this solution and then dried in air. One portion of the treated cloth was cured by immersion in water for 15 minutes at 50 C. and the other portion was cured by immersion in water to saturate the cloth and then heated EXA LE 7 in an oven for 5 minutes at 121 C. The resin add-ons obtained were 5.1 and 6.0% respectively. Thereafter the PF proceduredog i 1S gg zvlthltlfiatmg samples were tested for water repellency and compared prepare y C m 1 an F0 ylsocya' to an untreated control sample. The following results nates 1n the amounts shown in the following table. In each a were obtained. instance, the reaction temperatures and catalyst amounts are varied as necessary to obtain the indicated reaction Product Impact Spray Bag test products. In all cases, the treated paper 1s comparable to H H 0 d 24 6 8 P 0t 2 cure ass. that obtained and tested in Example 4. It 1s to be noted H2O plus oven heat cure 2&8 85 Pas; that 1n section II of the table, the polyrsocyanate used is Untreated 40.0 0 Fail. 21 20% by weight solution of the isocyanate:

Mols of modifier Amount of Amount of per mole modifier p0lyisocya-. equiv. of Modifier s) Polyisocyanate nate. (parts) NCO Section I:

A..- 1hexanethiol 8.7 Polymethylene polyphenlylsoeyanate 0.2 B- 1-decanoic acid. 19 do 50 0. 3 C- Benzoic acid. 4. 5 .do 50 O. 1 D- Heptyl amine 8.5 do 50 0.2 E- Dodecyl amine -do. 50 0.5 F- 4-(4hydroxyphenyl) butyl amine 12 do 50 0. 2 G-.. Formamide 12 -.do 50 0.7 H--. Benzamide 13.4 do 50 0.3 I N-heptylheptamide 17.8 do 50 0.2 Section II:

J l-eicosanol 30 Tris(isoeyanatophenyl)methane 185 1 14 do 920 0.2 11 d0 368 0.5 7 do 10 2 2 do 184 0.1 o a .-...do 46 0.4 P N-phenyl benzamide 2 ....do- 28 0.67 Q N-decyl dodecamide 3.5 do 37 0.5

EXAMPLE 8 An Octadecanol modified polyisocyanate was prepared as in Example 4. An emulsion of this product was prepared by combining the following components in the This emulsion contained about 10% solids. This emulsion was applied to kraft paper as in Example 4 and the cured and dried samples were tested for water repellency While there have been described various embodiments of the invention, the compositions and methods described are not intended to be understood as limiting the scope of the invention, as changes therewithin are possible and it is intended that each element recited in any of the following claims is to be understood as referring to all equivalent elements for accomplishing substantially the same results in substantially the same or equivalent manner, it being intended to cover the invention broadly in whatever form its principle may be utilized.

What is claimed is:

1. A method for rendering cellulosic materials waterrepellent which comprises contacting said cellulosic materials to be treated with an emulsion containing (a) water 19 a 3: (b) from about 0.3 to about 3 percent by weight of an alkali metal soap of a fatty acid containing from about 8 to about 26 carbon atoms (c) from'about 0.2 to about1.0 percent by weight of an-emulsifying agent selected from the group consisting of anionic alkyl and alkyl aryl sulfonates and sulfates containing from about 4 to about 30 carbon atoms in the alkyl portion and from about 6 to about 10 carbon atoms in the aryl portion, and

(d) from about 0.5 to about 50 percent by weight of a polyaryl polyisocyanate selected from the group consisting of (I) Hm i i and (II) Hm 0 N00 NiiR i V, v f

group consisting of halogen, hydrogen,Malky1 con;

taining from 1 to about 20 carbon atoms and alkoxy wherein the alkyl portion contains from 1 to about 20 carbon atoms; Y is selected from the group conbased on the weight of the cellulosic material. 1-4. A method, as claimedv in claim 1' wherein the tem drogen, phenyl, alkyl containing from about 20 carbon atoms, alkylphenol containing fromlto about 20 carbon atoms and, alkylphenonyalkoxy wherein the alkylphenoxy and alkoxy' groups each contain from 1 to about 20 carbon atoms.

2. A method as claimed in claim 1 wherein the emulsion contains soap in the amount of from about 0.5 to

0.005 percent, emulsifying" agent'ili famdiifitof from about 0.2 to about 0.002 percent and polyisocyanate in an amount of from about 10 to about 0.1 percent.

3. A- method as claimed in claim 1 wherein the resin add-on is from about 0.05 to about 50 percent by weight,

perature during the application of said emulsion is maintained at from about 20 to about C.

5. A method as claimed in claim 1 wherein the emulsion contains an organicsolvent.

6. A method as claimed in' claim 5 wherein the organic solvent is perchloroethylene. 1

References Cited Q N STATES -PATENTS UNITED 3,112,984 12/ 1963 Aldridge 8 416.2 3,294,713 12/ 1966 Hudson et al. 3,462,295 8/1969 Elmquist ,et al. 3,505,001 4/1970 Wagner 8 l16.2

GEORGE F. LESMES, Primary Examiner I CANNON, Assistant Examiner US. 01. X.R.

.8DIG 11; 106-2; 117-1355 143, 144, 147, 154; %3165, 250-?9 R i UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTEON Patent No. 3 672 ,818 Dated June 27 ,l972

IHVntOY(S) George M. Wagner and William J. Vullo It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column '2 line 57 "p is 0 to 1" should read ---p is 'O or l--.

Column 7 formula 2:

II II should read Column 9 formula 3:

/ -CH v 2 should read CH. a

Column 9, formula 6:

"H C should read H 0 Column 19 Claim 1 line 15: v

cx should read Signed and sealed this 19th day of December 1972.

(SEAL) Attest:

EDWARD M.FLETCHER, JR. ROBERT GOTTSCHALK Attestlng Officer Commissioner of Patents FORM PC4050 (1069) v USCOMM-DC 60376-P69 9 [L54 GOVERNMENT PRINTING OFFICE 2 959 0-356-33, 

